Modification of the optical and structural properties of ZnO nanowires by low-energy Ar+ ion sputtering
© Allah et al.; licensee Springer. 2013
Received: 4 February 2013
Accepted: 23 March 2013
Published: 9 April 2013
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© Allah et al.; licensee Springer. 2013
Received: 4 February 2013
Accepted: 23 March 2013
Published: 9 April 2013
The effects of low-energy (≤2 kV) Ar+ irradiation on the optical and structural properties of zinc oxide (ZnO) nanowires (NWs) grown by a simple and cost-effective low-temperature technique were investigated. Both photoluminescence spectra from ZnO NW-coated films and cathodoluminescence analysis of individual ZnO NWs demonstrated obvious evidences of ultraviolet/visible luminescent enhancement with respect to irradiation fluence. Annihilation of the thinner ZnO NWs after the ion bombardment was appreciated by means of high-resolution scanning electron microscopy and transmission electron microscopy (TEM), which results in an increasing NW mean diameter for increasing irradiation fluences. Corresponding structural analysis by TEM pointed out not only significant changes in the morphology but also in the microstructure of these NWs, revealing certain radiation-sensitive behavior. The possible mechanisms accounting for the decrease of the deep-level emissions in the NWs with the increasing irradiation fluences are discussed according to their structural modifications.
The outstanding and novel physical properties determined in zinc oxide (ZnO) nanowire (NW) special shapes and structures are the reason for which nanoscale one-dimensional semiconductor materials have attracted much attention in recent years . ZnO NWs are very promising as a consequence of their direct bandgap of 3.37 eV (at room temperature) and an exciton binding energy, 60 meV, larger than their thermal energy at room temperature (RT) that enables the observation of excitonic emission at RT. Because of this, they can be used for a wide range of applications such as ultraviolet (UV) light-emitting devices , nanogenerators , rectifying diodes , sensors , and electron emitters .
Many techniques offer the possibility to obtain ZnO NWs, such as metal-organic chemical vapor deposition, vapor phase epitaxy, direct carbo-thermal growth, and pulsed laser deposition [7, 8]. However, all these techniques require low pressures and high operating temperatures (800°C to 1,400°C). Recently, the hydrothermal synthesis route has been successfully applied to the growth of ZnO nanostructures at lower temperature [9–12]. However, despite its easy implementation, the growth rate  and the optical quality of the resultant as-grown ZnO nanostructures are generally poorer than those grown by the other techniques, and the technique offers low reproducibility (size and shape control) [14, 15]. Our group and other researchers have already reported on the successful growth of high-quality ZnO NWs using a simple technique consisting in the oxidation of Zn metal films in ambient conditions [16–22]. The simplicity of the process, the low temperature required (close to 500°C), as well as the good quality of the obtained NWs make this method attractive for future nanodevice applications.
It is noteworthy that many reports on the optical properties of ZnO nanorods and NWs point out to the apparition of a deep-level emission (DLE) band in the visible, together with the near-band edge emission (NBE) in the UV. In this sense, to change their optical properties, several studies on emission tailoring of ZnO NWs exposed to an irradiation source have already been developed [23–25] but with contradictory outcomes. In particular, with regard to the optical response, Krishna and co-workers reported the occurrence of several bands in the visible region which were identified in the PL spectra of 15-keV energy Ar+-irradiated thin films. They indicated a strong detraction of the visible signal with respect to the UV emission , and similar optical results were confirmed by Liao and co-authors in the case of 5 to 10 kV Ti-implanted ZnO NWs . Besides the modification of the UV/visible intensity ratio, UV signal blueshift was found by Panigrahy for 2- to 5-keV Ar+-irradiated ZnO nanorods . The UV blueshift was also detected in the cathodoluminescence (CL) spectra of ZnO NWs irradiated with 30-keV Ti+ ions. Nevertheless, in this case, the visible emission did not suffered changes with the implantation doses , contrary to the behavior observed by Wang et al.  who reported a complete disappearance of the visible emission from ZnO NWs irradiated with 2-keV H+ ions. Hence, the modification of the luminescence properties of ZnO after irradiation experiments is still not clearly understood and, even less, after low energy irradiation experiments. In any case, it would be desired to tailor the ZnO NW emission by minimizing the visible emission and therefore improving the UV luminescence. This would be particularly important in the case of cost-effective growth procedures, for which the obtained ZnO NWs could present some important emissions in this spectral range.
In this work, we present the results of exposing ZnO NWs to a low-energy (≤2 kV) Ar+ ion irradiation. These experiments require a relatively simple experimental setup where only a small high-vacuum chamber and an ion gun are needed. Our experimental results show that the irradiation gives rise to an increase of the UV emission with respect to the visible one. We base the explanation of these effects on the structural analysis performed on individual NWs. From these results, we conclude that low-energy Ar+ ion irradiation is a promising method to tailor the luminescent properties of ZnO NWs.
For the growth of the ZnO NWs, LiNbO3 (LN) substrates were chosen, motivated first by the absence of interaction between the substrate (LN) and the ZnO films, demonstrated in our previous unpublished experiments, and second, the suitability of the LN/ZnO system for the development of various applications such as surface acoustic wave gas sensor devices [31, 32]. The c-axis-oriented LN substrates used in this work were grown in our laboratory by the standard Czochralski technique. LN substrates of about 1 mm thick were cut perpendicular to the c-axis. A Zn metal film was evaporated at 800°C on top of the LN substrates. The evaporation took place for 5 min inside a quartz ampoule located in a horizontal furnace. Only the Zn (6N), 0.5755 g, pellets were heated, keeping the LN substrate close to RT during this evaporation step. A further oxidation step was performed in air at 500°C. This process was stopped after about 23 h, when the Zn film thickness reached values near to 30 μm, as deduced by means of profilometry measurements. This technique has already been successfully used to grow high-quality ZnO NWs on other substrates such as CdTe . The obtained NWs grow on top of the ZnO films formed by the oxidation of the Zn film evaporated layer. More details of the preparation technique can be found elsewhere . After confirming the formation of a quite homogenous NW cover layer on the sample, several areas were independently irradiated with different Ar+ ion beam fluences. The Ar+ irradiation took place inside a home-made high-vacuum (10−6 mbar) chamber system equipped with a Specs IQE-11 broad beam ion gun (Berlin, Germany). Irradiation energies of 500 and 2,000 V were used, which result in fluences of 1.5 × 1016 cm−2 and 1017 cm−2, respectively (the irradiation time was always 1 h).
High-resolution scanning electron microscopy (HR-SEM) analyses were carried out by using a Philips SEM-FEG-XL30 microscope (Amsterdam, the Netherlands). Energy-dispersive X-ray in SEM mode (EDX-SEM) analysis was performed in a SEM microscope (Hitachi S-3000 N, Chiyoda, Tokyo, Japan), with an attached EDX analyzer (Oxford Instruments, model INCAxsight, Abingdon, Oxfordshire, UK). CL measurements were carried out at liquid nitrogen temperature (80 K) using a XiCLone (Gatan, UK) module attached to a LEO 1530-Carl Zeiss-FESEM microscope (Oberkochen, Germany). The luminescence signal was detected with a Peltier-cooled CCD (Photometrics Ltd., Tucson, AZ, USA). Micro-photoluminescence (μPL) measurements at RT were obtained with a HRLabRam spectrometer (HORIBA Jobin Yvon Inc., Edison, NJ, USA) attached to a metallographic microscope. The excitation was done with a He-Cd laser line at 325 nm, through a ×40 microscope objective, which also collected the scattered light. Conventional transmission electron microscopy (CTEM) and high-resolution transmission electron microscopy (HR-TEM), as well as EDX spectroscopy in scanning transmission electron microscopy (TEM) mode, were realized using a JEOL 1200 EX (JEOL Ltd., Akishima, Tokyo, Japan) and a 2010 F microscope operating at 120 and 200 kV, respectively. The latter is equipped with an Oxford Instruments’ EDX detector. For these measurements, the NWs were scraped from the substrate and dispersed on a lacey carbon-coated copper grid.
Before any structural or optical characterization, the irradiated areas were observed by the naked eye when illuminating under UV light (at 365 and 254 nm). A clear color change was detected with respect to the unirradiated areas; the irradiated ones appear black (not shown here, see Additional file 2). This was the first evidence of an important change in the optical emission properties of the samples, which motivated a detailed optical characterization of the irradiated structures.
The deconvolution of the visible bands gives two main contributions at 2.05 and 2.30 eV - a residual contribution at 1.83 eV is also observed - being 2.30 eV as the predominant one (see Figure 2). The spectral position of these bands would indicate a contribution from both the GL and the YL emissions. As we can see in the figure, the irradiation seems to affect mainly the GL emissions with a strong reduction of this contribution with the increase of the fluence. Consequently, a tiny redshift is observed in the broad band of the visible emission. Normalizing the NBE emission band, it is observed that the ratio between the NBE and visible emissions increases in the irradiated areas, the increase being more pronounced when the irradiation fluence increases. Thus, the low-energy (≤2 kV) Ar+ irradiation brings about a rearrangement of the ZnO lattice with a reduction of the DLE and a relative increase of the NBE transition (excitons).
The differences in the observed luminescence bands between μPL and CL spectra can be a consequence of the different excitation conditions used in both kinds of measurements. Indeed, some authors have reported noticeable differences in the shape of the visible band in ZnO NWs depending on the PL excitation conditions . Since the relative intensity of the defect emission bands can be significantly affected by the excitation power conditions and taking into account the controversial results reported in the literature for the different contributions (GL, YL, and RL) , caution needs to be taken to assign an exact origin for the DLEs in our NWs as well as to explain the changes observed between the μPL and CL results. From all these considerations, the main conclusion from our analysis is the diminution of the DLE with respect to the NBE in the NWs with the increase of the irradiation fluence.
Nevertheless, if the visible emission is supposed to be mainly originated from defects related to the surface, other factors apart from the annihilation of the thinnest NWs might also be considered. Both μPL and CL data reveal an enhancement of the UV/visible ratio with the increase of the irradiation fluence. Certainly, a reduction of the point defect density in the surface would also result in the UV emission enhancement as a consequence of a net reduction of the visible emission. Perhaps, surface diffusion and annealing effects due to a temperature increase induced during the irradiation process could favor it in some way . However, it is important to mention that the thermal changes near the sample surface were measured during the irradiation processes by a thermocouple installed in the sample holder inside the irradiation chamber. The temperature of the sample only increase up to 60°C during the irradiation, so it is not expected that thermal changes deeply affect to the point defect removal.
It is more likely that the irradiation process can activate a point defect movement, giving rise to a close pair recombination by point defect migration. These diffusion processes have also been known to have important effects on the surface structure, even inducing nanopatterning after low-energy ion irradiation [49, 50]. Hence, the effect of the Ar+ ions can cause the displacement of Zn atoms from their sites either when they are located as native interstitials or in their equilibrium positions inside the ZnO lattice. This is due to their lower displacement energy compared to that of the oxygen atoms (energy displacement of Zn and O are 18.5 and 41.4 eV, respectively) . Additionally, part of the Zn removed would subsequently segregate towards the surface, favored by their high mobility even at RT [52, 53], contributing to the shell structure observed in the HR-TEM images. Indeed, other authors have also reported such Zn segregation to the surface due to the irradiation process, accompanied by a color change ; the latter is in agreement with our observations with the naked eye under UV illumination. In our case, we have not detected the presence of metallic Zn even if the color change was evident; these results may not be too surprising taking into account the strong Zn tendency to form oxides when in contact with oxygen, avoiding its TEM observation. Besides, the proposed Zn migration due to the irradiation process can result in a restructuration/reduction of many existing defects, which can effectively passivate deep-level intrinsic defects in the ZnO NWs and consequently decreases the DLE intensity with respect to the NBE emission of the individual NWs. This could explain the increase of the intensity UV/visible ratio showed in the CL spectra where the NWs analyzed (irradiated or not) presented different CL spectra being dimensionally comparable.
Both mechanisms, the annihilation of the thinner NWs and the reduction of defect concentration with the increase of the irradiation fluence, would support the found increase of the intensity ratio between the NBE and the visible emission. Both can work in cooperation and also would explain the good fitting of Shalish’s size-dependent rule and the increase of the C parameter. However, further works are needed to clarify the effects of low-energy (≤2 kV) Ar+ irradiation on the optical and structural properties of ZnO nanowires.
Micro-photoluminescence and cathodoluminescence measurements have shown that the irradiation of ZnO NWs with low-energy (≤2 kV) Ar+ ions enhances the UV/visible intensity ratio. TEM analysis demonstrated significant changes in the morphology as well as in the microstructure of these NWs, revealing a certain radiation-susceptible nature. HR-TEM studies revealed the loss of thinner NW families and the existence of NWs with surface modifications due to the irradiation with low-energy Ar+ ions. We postulate that Ar+ ion irradiation would annihilate the thinner ZnO NWs as well as activate Zn diffusion, leading to a restructuration/reduction of many native defects. We attribute the attenuation of the visible emission both to Zn diffusion effect and to the reduction of surface-related volume responsible for the deep-level luminescence. This work demonstrates that an inexpensive technique can improve the luminescent behavior of ZnO NWs grown by a cost-effective technique based on Zn oxidation under low temperature in ambient conditions.
Conventional transmission electron microscopy
Fast Fourier transform
High-resolution scanning electron microscopy
High-resolution transmission electron microscopy
Near-band edge emission
Transmission electron microscopy
This work has been supported by the MICINN (project no. MAT2010-15206) and the EU (COST Action MP0805).
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